C3 to C5 polyfluorcalkanes propellants

ABSTRACT

Polyfluoroalkanes are used as propellants in sprayable compositions or in the the preparation of plastic foams and in the electrical industry as cleansing and degreasing agents.

This application is a division, of application Ser. No. 07/469,622 filed Jan. 24, 1990 which is now U.S Pat. No. 5,496,866.

The present invention relates to the use of C₃ to C₅ polyfluoroalkanes comprising at least two fluorine atoms as propellents, especially for aerosols and in the production of plastic foams.

The use of fluorochlorohydrocarbons, for example trichlorofluoromethane, dichlorodifluoromethane and trichlorofluoroethane, as propellents for the above purposes, is known. According to more recent studies, the chlorine content of conventional propellents damages the ozone layer of the earth's atmosphere (see J. F. D. Mills, Cell. Polym. 5, 343 (1987) and F. S. Rowland et el., Nature 239, 8 (1974)); for this reason limits have been specified for the amounts of fluorochlorohydrocarbons produced. The need has therefore arisen for chlorine-free propellents.

We have now found that those polyfluoroalkanes of the formula

    CX.sub.3 --CY.sub.2 --R                                    (I),

wherein

the radicals X located on the same carbon atom stand for hydrogen and/or fluorine,

the radicals Y located on the same carbon atom stand for hydrogen, fluorine and/or CF₃, and

R stands for CH₂ F, CHF₂, CH₃, CF₃, CF₂ --CH₃, CF₂ CH₂ F, CH₂ --CH₃, CH₂ --CH₂ --CH₃ or --CH(CH₃)--CH₃,

and wherein the polyfluoroalkanes of the formula (I) contain at least two fluorine atoms, can be used advantageously as propellants.

Those polyfluoroalkanes of the formula (I) are preferred which contain 3 to 7, particularly 4 to 6 fluorine atoms.

Furthermore, those polyfluoroalkanes of the formula (I) are preferred in which the CX₃ group represents a CF₃, CHF₂ or CH₃ group and the CY₂ group represents a CH₂, CHF, CF₂ or C(CF₃)H group.

For the use according to the invention, those individual compounds conforming to formula (I) in which X₃, Y₂ and R are present in one of the combinations listed in Table 1, are particularly preferred.

                  TABLE 1                                                          ______________________________________                                         X.sub.3     Y.sub.2     R                                                      ______________________________________                                         F.sub.3     H.sub.2     CH.sub.2 F                                             F.sub.3     HF          CH.sub.2 F                                             F.sub.3     H.sub.2     CHF.sub.2                                              HF.sub.2    F.sub.2     CH.sub.2 F                                             F.sub.3     HF          CH.sub.3                                               H.sub.3     F.sub.2     CH.sub.3                                               F.sub.3     F.sub.2     CF.sub.2 --CH.sub.3                                    F.sub.3     HF          CF.sub.2 --CH.sub.3                                    F.sub.3     H.sub.2     CF.sub.2 --CFH.sub.2                                   F.sub.3     H.sub.2     CH.sub.2 --CH.sub.3                                    H.sub.3     F.sub.2     CF.sub.2 --CH.sub.3                                    F.sub.3     H.sub.2     CF.sub.2 --CH.sub.3                                    F.sub.3     HCF.sub.3   CH.sub.3                                               F.sub.3     H.sub.2     CH.sub.2 --CH.sub.2 --CH.sub.3                         F.sub.3     H.sub.2     --CH(CH.sub.3)--CH.sub.3                               F.sub.3     H.sub.2     CF.sub.3                                               ______________________________________                                    

The methods for preparing the polyfluoroalkanes for use according to the invention are known (see, for example, Zh. Org. Khim. 1980, 1401-1408 and 1982, 946 and 1168; Zh. Org. Khim. 1988, 1558; J. Chem. Soc. Perk. 1, 1980, 2258; J. Chem. Soc. Perk. Trans. 2, 1983, 1713; J. Chem. Soc. C 1969, 1739; Chem. Soc. 1949, 2860; Zh. Anal. Khim. 1981 36 (6), 1125; J. Fluorine Chem. 1979, 325; Izv. Akad. Nauk. SSSR, Ser. Khim. 1980, 2117 (in Russian); Rosz. Chem. 1974 (48), 1697 and J. A. C. S. 67, 1195 (1945), 72, 3577 (1950) and 76, 2343 (1954)).

The propellants for use according invention are particularly suitable for aerosols and production of plastic foams; the individual compounds of the formula (I), mixtures of compounds of the formula and mixtures of compounds Of the formula (I) with conventional propellants may be used for this purpose. Individual compounds of the formula (I) or mixtures of compounds of the formula (I) are preferred.

Suitable aerosols are those employed for cosmetic and medicinal purposes, for example deodorant aerosols, anti-asthma sprays end liquid plaster sprays. Aerosols which employ the propellants for use according to the invention, are distinguished by the fact that the propellant is inert and the ozone layer of the earth's atmosphere is no longer negatively affected by the corresponding amount of propellants according to the invention, since they are chlorine-free.

The methods of producing plastic foams using propellants is generally known. In the production of closed-cell foams the propellants may also act as heat-insulating cellular gases. This is also true for the propellants for use according to the invention.

The propellants for use according to the invention may be employed, for example, in the production of foams based on isocyanates, polystyrenes, polyvinyl chlorides end phenol-formaldehyde condensates. They are preferably used in the production of foams based on isocyanates, in particular in the production of polyurethane and/or polyisocyanurate foams they are especially preferred in the production of rigid foams based on isocyanates.

The production of foams based on isocyanates is known per se and is described, for example, in German Offenlegungsschriften 1,694,142, 1,694,215 and 1,720,768, as well as in Kunststoff-Handbuch [Plastics Handbook], volume VII, Polyurethane, edited by Viewag and Hochtlen, Carl Hanser Verlag, Munich 1966, and in the new edition of this tome, edited by G. Oertel, Carl Hanser Verlag, Munich, Vienna, 1983.

These foams are mainly those comprising urethane and/or isocyanurate and/or allophanate and/or uretdione and/or urea and/or carbodiimide groups.

The following can be employed for the production of foams based on isocyanates, using propellants according to the invention:

a) As starting components altphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those described, for example, by W. Siefken in Justus Liebigs Annalan der Chemie, 562, pp. 75-136, for example those of the formula

    Q(NCO).sub.n

in which

n denotes 2-4 ,preferably 2-3, and

Q denotes an aliphatic hydrocarbon radical of 2-18, preferably 6-10 carbon atoms, a cycloaliphatic hydrocarbon radical of 4-15, preferably 5-10 carbon atoms, an aromatic hydrocarbon radical of 6-15, preferably 6-13 Carbon atoms or an arallphatic hydrocarbon radical of 8-15, preferably 8-13 carbon atoms, for example such polyisocyanates as described in DE-OS 2,832,253, pp. 10-11. Particularly preferred are usually those polyisocyanates which are technically readily accessible, for example the 2,4- and 2,6-toluylene diisocyanate as well as any mixture of these isomers ("TDI"); polyphenylpolymethylenepolyisocyanates, such as those obtained by an aniline-formaldehyde condensation end subsequent treatment with phosgene ("crude MDI"), and polyisocyanates comprising carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("modified polyisocyanates"), especially those modified polyisocyanates which are derived from 2,4- and/or 2,6-toluylene diisocyanate and from 4,4'- and/or 2,4'-diphenylmethane diisocyanate.

b) The starting components may further be compounds of a molecular weight usually of 400 to 10,000, containing at least two hydrogen atoms reactive toward isocyanates. These comprise, besides compounds containing amino, thio or carboxyl groups, preferably compounds containing hydroxyl groups, in particular compounds containing 2 to 8 hydroxyl groups, especially those of a molecular weight of 1,000 to 6,000, preferably 2,000 to 6,000, for example polyethers and polyesters as well as polycarbonates and polyester amides containing at least 2, usually 2 to 8, preferably 2 to 6 hydroxyl groups; these compounds are known per se for the preparation of homogeneous and cellular polyurethanes and are disclosed, for example, in DE-OS 2,832,253, pp. 11-18.

c) When appropriate, compounds comprising at least two hydrogen atoms reactive toward isocyanates and of a molecular weight of 32 to 399 maybe used as further starting components. Also in this case compounds containing hydroxyl groups and/or amino groups and/or thiol groups and/or carboxyl groups, preferably compounds containing hydroxyl groups and/or amino groups, are understood to be those which are used as chain lengtheners or crosslinking agents. These compounds usually have 2 to 8, preferably 2 to 4 hydrogen atoms reactive toward isocyanates. Appropriate examples are disclosed in DE-OS 2,832,253, pp. 19-20.

d) One polyfluoroalkane or several polyfluoroalkanes of the formula (I) as propellant and insulating gas, if appropriate in admixture with conventional propellents and insulating gases.

e) When appropriate, other auxiliary agents and additives may be used at the same time, such as

water and/or other highly volatile organic substances as propellants,

additional catalysts of the type known per se in amounts up to 10% by weight, based on the component b),

surface-active additives, such as emulsifiers and foam stabilizers,

reaction retardants, for example acidic substances such as hydrochloric acid or organic acid halides, also cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes and other flame retardants of the type known per se, for example tricresyl phosphate, also stabilizers against the effects of ageing and weathering, plasticizers and fungistats and bacteriostats as well as fillers such as barium sulphate, kieselguhr, carbon black or whiting.

Other examples of surface active additives, foam stabilizers, cell regulators, reaction retardants, stabilizers, flame retardants, plasticizers, dyes, fillers, fungistats, bacteriostats to be used at the same time if appropriate, as well as details concerning the use and action of these additives are described in Kunststoff-Handbuch [Plastics Handbook], volume VII, edited by Viewag and Hochtlen, Carl Hanser Verlag, Munich 1966, for example on pages 103-113.

The isocyanate-based foams can be prepared in a manner known per se.

The preparation of polyurethane plastics may be prepared, for example, as follows: the reactants are caused to react by the single-stage process known per se, the prepolymer process or the semiprepolymer process, frequent use being made of plant machinery, for example that disclosed in U.S. Pat. No. 2,764,565. Details concerning the processing plant which are likewise relevant according to the invention, are described An Kunststoff-Handbuch, volume VII, edited by Viewag and Hochtlen, Carl Hanser Verlag, Munich 1966, for example on pages 121 to 205.

According to the invention it is also possible to produce cold-curing foams (cf. GB-PS 1,162,517, DE-OS 2,153,086).

Foams may of course also be produced by block foaming or by the double conveyor belt process known per se.

The products obtainable according to the invention may be used, for example, as insulation panels for roof insulation.

In foam production, the propellents for use according to the invention may be employed, for example, in amounts of 1 to 30% by weight, preferably 2 to 10% by weight, in each case based on the foam.

Compared with conventional foams of similar or virtually identical cell structure, foams produced by propellents for use according to the invention are distinguished by the fact that in their production, application and disposal they no longer negatively affect the ozone layer of the earth's atmosphere by the responding amount of the propellents according to the invention.

Polyfluoroalkanes of the formula (I) may be further employed as degreasing and cleansing agents in the electrical industry. The same polyfluoroalkanes are preferred for this purpose as those referred to above as being preferred. Here, too, the individual compounds of the formula (I), mixtures of compounds of the formula (I) and mixtures of compounds of the formula (I) with conventional degreasing and cleansing agents may be employed.

EXAMPLE 1

100 g of a polyether with a hydroxyl value of 380, which has resulted from the addition of propylene oxide to a solution of saccharose, propylene glycol and water,

2 g of a siloxane polyether copolymer as foam stabilizer,

3.8 g of water and

3 g of dimethylcyclohexylamine were mixed.

100 g of this mixture were thoroughly mixed with

15 g of 1,1,1,3,3,3-hexafluoro-2-methylpropane as propellant, using a laboratory stirrer.

This mixture was foamed with 152 g of crude 4,4'-diisocyanatodiphenylmethane. A rigid polyurethane foam was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):     10                                                     Setting time (s):       42                                                     Free density (kg/m.sup.3):                                                                             24                                                     Cell structure:         fine                                                   ______________________________________                                    

EXAMPLE 2

100 g of a polyether with a hydroxyl value of 380 which results from the addition of propylene oxide to a solution of saccharose, propylene glycol and water,

2 g of a siloxane polyether copolymer as foam stabilizer,

3.8 g of water and

3 g of dimethylcyclohexylamine were mixed.

100 g of this mixture were thoroughly mixed with

15 g of 1,1,1,3,3,3-hexafluoropropane as propellant, using a laboratory stirrer.

This mixture was foamed with 152 g of crude 4,4'-diisocyanatodiphenylmethane. A rigid polyurethane foam was obtained. Foam and physical data:

    ______________________________________                                         Induction time (s):     10                                                     Setting time (s):       40                                                     Free density (kg/m.sup.3):                                                                             22                                                     Cell structure:         fine.                                                  ______________________________________                                    

EXAMPLE 3

100 g of a polyether with a hydroxyl value of 380 which results from the addition of propylene oxide to a solution of saccharose, propylene glycol and water,

2 g of a siloxane polyether copolymer as foam stabilizer,

3.8 g of water and

3 g of dimethylcyclohexylamine were mixed.

100 g of this mixture were thoroughly mixed with

15 g of 2,2,4,4-tetrafluorobutane as propellant, using a laboratory stirrer.

This mixture was foamed with 152 g of crude 4,4'-diisocyanatodiphenylmethane. A rigid polyurethane foam was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):     10                                                     Setting time (s):       39                                                     Free density (kg/m.sup.3):                                                                             21                                                     Cell structure:         fine.                                                  ______________________________________                                    

EXAMPLE 4

60 g of a polyether with a hydroxyl value of 950 which resulted from the addition of propylene oxide to trimethylpropane,

40 g of a polyether with a hydroxy value of 56 which resulted from the addition of propylene oxide to trimethylpropane,

0.5 g of water and

2 g of a siloxane polyether copolymer as foam stabilizer were mixed.

100 g of this mixture was thoroughly mixed with

10 g of 1,1,1,3,3,3-hexafluoro-2-methylpropane as propellant, using a laboratory stirrer.

This mixture was foamed with 164 g of crude 4,4'-diisocyanatodiphenylmethane. A rigid solid polyurethane plastic was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):        75                                                  Setting time (s):         120                                                  Free density (kg/m.sup.3):                                                                                75                                                  Total density compacted (kg/m.sup.3):                                                                    350                                                  Cell structure:           fine.                                                ______________________________________                                    

EXAMPLE 5

60 g of a polyether with a hydroxyl value of 950 Which resulted from the addition of propylene oxide to trimethylpropane,

40 g of a polyether with a hydroxy value of 56, which resulted from the addition of propylene oxide to trimethylolpropane,

0.5 g of water and

2 g of a siloxane polyether copolymer as foam stabilizer were mixed.

100 g of this mixture were thoroughly mixed with

10 g of the 1,1,1,3,3,3-hexafluoropropane according to the invention as propellant, using a laboratory stirrer.

This mixture was foamed with 164 g of crude 4,4'-diisocyanatodiphenylmethane. A rigid solid polyurethane plastic was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):        88                                                  Setting time (s):         136                                                  Free density (kg/m.sup.3):                                                                                70                                                  Total density compacted (kg/m.sup.3):                                                                    350                                                  Cell structure:           fine.                                                ______________________________________                                    

EXAMPLE 6

60 g of a polyether with a hydroxyl value of 950 which resulted from the addition of propylene oxide to trimethylolpropane,

40 g of a polyether with a hydroxyl value of 56 which resulted from the addition of propylene oxide to trimethylolpropane,

0.5 g of water and

2g of a siloxane polyether copolymer as foam stabilizer were mixed.

100 g of this mixture were thoroughly mixed with 10 g of 2,2,4,4-tetrafluorobutane as propellant, using a laboratory stirrer.

This mixture was foamed with 164 g of crude 4,4'-diisocyanatodiphenylmethane. A rigid solid polyurethane plastic was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):        83                                                  Setting time (s):         138                                                  Free density (kg/m.sup.3):                                                                                68                                                  Total density compacted (kg/m.sup.3):                                                                    350                                                  Cell structure:           fine.                                                ______________________________________                                    

EXAMPLE 7

91 of a polyether with a hydroxyl value of 56 which resulted from the addition of propylene oxide to trimethylolpropane,

9 of monoethylene glycol and

0.1 g of water were mixed.

100 g of this mixture were thoroughly mixed with

15 g of 1,1,1,3,3,3-hexafluoro-2-methylpropane as propellant, using a laboratory stirrer.

This mixture was foamed with 56 g of crude 4,4'-diisocyanatodiphenylmethane. A tough and resilient polyurethane foam was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):        33                                                  Setting time (s):         112                                                  Free density (kg/m.sup.3):                                                                               131                                                  Total density compacted (kg/m.sup.3):                                                                    350                                                  Cell structure:           fine.                                                ______________________________________                                    

EXAMPLE 8

91 g of a polyether with a hydroxyl value of 56, which resulted from the addition of propylene oxide to trimethylolpropane,

9 g of monoethylene glycol and

0.1 g of water were mixed.

100 g of this mixture were thoroughly mixed with

15 g of 1,1,1,3,3,3-hexafluoropropane as propellant, using a laboratory stirrer.

This mixture was foamed with 56 g of crude 4,4'-diisocyanatodiphenylmethane. A tough and resilient polyurethane foam was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):      36                                                    Setting time (s):       108                                                    Free density (kg/m.sup.3):                                                                             121                                                    Cell structure:         fine.                                                  ______________________________________                                    

EXAMPLE 9

91 g of a polyether with a hydroxyl value of 56, which resulted from the addition of propylene oxide to trimethylolpropane,

9 g of monoethylene glycol and

0.1 g of water were mixed.

100 g of this mixture were thoroughly mixed with

15 g of 2,2,4,4-tetrafluorobutane as propellant, using a laboratory stirrer.

This mixture was foamed with 56 g of crude 4,4'-diisocyanatodiphenylmethane. A tough and resilient polyurethane foam was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):      38                                                    Setting time (s):       108                                                    Free density (kg/m.sup.3):                                                                             117                                                    Cell structure:         fine                                                   ______________________________________                                    

EXAMPLE 10

100 g of e polyether with a hydroxyl value of 56, which resulted from the addition of propylene oxide to trimethylolpropane,

3 g of water,

1 g of-a siloxane polyether copolymer as foam stabilizer,

0.05 g of dibutyltin dilaurate were mixed.

100 g of this mixture were thoroughly mixed with

10 g of 1,1,1,3,3,3-hexafluoro-2-methylpropane as propellants, using a laboratory stirrer.

This mixture was foamed with 41 g of toluylene diisocyanate. A flexible polyurethane foam was obtained. Foaming and physical dates

    ______________________________________                                         Induction time (s):      8                                                     Setting time (s):       105                                                    Free density (kg/m.sup.3):                                                                              28                                                    Cell structure:         fine.                                                  ______________________________________                                    

EXAMPLE 11

100 g of a polyether with a hydroxyl value of 56, which resulted from the addition of propylene oxide to trimethylolpropane,

3 g of water,

1 g of a siloxane polyether copolymer as foam stabilizer,

0.05 g of dibutyltin dilaurate were mixed.

100 g of this mixture were thoroughly mixed with

10 g of 1,1,1,3,3,3-hexafluoropropane as propellant, using a laboratory stirrer.

This mixture was foamed with 41 g of toluylene diisocyanate. A flexible polyurethane foam was obtained. Foaming end physical data:

    ______________________________________                                         Induction time (s):      8                                                     Setting time (s):       103                                                    Free density (kg/m.sup.3):                                                                              26                                                    Cell structure:         fine.                                                  ______________________________________                                    

EXAMPLE 12

100 g of a polyether with a hydroxy value of 56, which resulted from the addition of propylene oxide to trimethylolpropane,

3 g of water,

1 g of a siloxane polyether copolymer as foam stabilizer,

0.05 g of dibutyltin dilaurate were mixed.

100 g of this mixture were thoroughly mixed with

10 g of 2,2,4,4-tetrafluorobutane as propellant, using a laboratory stirrer.

This mixture was foamed with 41 g of toluylene diisocyanate. A flexible polyurethane foam was obtained. Foaming and physical data:

    ______________________________________                                         Induction time (s):      8                                                     Setting time (s):       108                                                    Free density (kg/m.sup.3):                                                                              25                                                    Cell structure:         fine.                                                  ______________________________________                                     

What is claimed is:
 1. A method of forming plastic foam compositions comprising foaming a plastic based on isocyanate in the presence of a propellant the improvement wherein the propellant comprises a polyfluoroalkane of the formula:

    CHF.sub.2 --CF.sub.2 --CFH.sub.2.


2. 2. A closed cell plastic foam composition prepared by foaming a plastic material based on isocyanate in the presence of a propellant the improvement wherein the propellant comprises a polyfluoroalkane of the formula:

    CHF.sub.2 --CF.sub.2 --CFH.sub.2. 